Hydrogen Peroxide → Bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

HRID 133632

Reaktionsgleichung

Reaktionsgleichung von HRID 133632
CS(O)(=O)=O.[C:6]([O:30][CH:31]1[CH2:36][C:35]([CH3:38])([CH3:37])[N:34]([OH:39])[C:33]([CH3:41])([CH3:40])[CH2:32]1)(=[O:29])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]([O:17][CH:18]1[CH2:23][C:22]([CH3:25])([CH3:24])[N:21]([OH:26])[C:20]([CH3:28])([CH3:27])[CH2:19]1)=[O:16].OO.S([O-])([O-])=O.[Na+].[Na+].[CH2:50]1[CH2:55][CH2:54][CH2:53][CH2:52][CH2:51]1>O.CS(O)(=O)=O.C(#N)C>[C:6]([O:30][CH:31]1[CH2:32][C:33]([CH3:41])([CH3:40])[N:34]([O:39][CH:50]2[CH2:55][CH2:54][CH2:53][CH2:52][CH2:51]2)[C:35]([CH3:38])([CH3:37])[CH2:36]1)(=[O:29])[CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]([O:17][CH:18]1[CH2:19][C:20]([CH3:27])([CH3:28])[N:21]([O:26][CH:50]2[CH2:55][CH2:54][CH2:53][CH2:52][CH2:51]2)[C:22]([CH3:24])([CH3:25])[CH2:23]1)=[O:16]

Komponenten

9

Edukt 5

HCID 784Hydrogen PeroxideHCID 6395Methanesulfonic Acid2×HCID 8078CyclohexaneHCID 24437Sodium SulfiteHCID 11272241Bis(1-hydroxy-2,2,6,6-tetramethyl-4-piperidinyl)decandioate

Produkt 1

HCID 18716452Bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacateAusbeute 43 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 6395Methanesulfonic AcidKatalysatorHCID 962WaterLösungsmittel3×HCID 6342AcetonitrileLösungsmittel

Reaktionsbedingungen

Temperatur
55 °C

Versuchsvorschrift

A solution of 0.268 g (0.964 mmol) of ferrous sulfate heptahydrate and 0.350 g (3.64 mmol) of methanesulfonic acid in 3.7 g of water is added to a mixture of 10.3 g (20.2 mmol) of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 110 ml of acetonitrile, and 60 ml of cyclohexane. The mixture is heated to 55° C. A solution of 11.0 g (162 mmol) of 50% aqueous hydrogen peroxide is added dropwise to the reaction mixture over 4.75 hours while the reaction temperature is brought to and maintained at reflux. A solution of 0.098 g of ferrous sulfate heptahydrate and 0.128 g of methanesulfonic acid in 0.3 g of water is added to the reaction mixture 2.25 hours after the peroxide addition is started. A solution of 0.053 g of ferrous sulfate heptahydrate and 0.070 g of methanesulfonic acid in 0.4 g of water is added to the reaction mixture 4 hours after the peroxide addition is started. After all the peroxide is added, the reaction mixture is heated at reflux for 45 minutes. The reaction mixture is allowed to cool slowly to room temperature while stirring is continued. Peroxide is decomposed by the addition of 4.5 g of sodium sulfite. The aqueous layer is discarded, and after concentration of the organic solution, the crude product is purified by flash chromatography on silica gel with 20:1 heptane-ethyl acetate to afford 5.9 g (43% yield) of the title compound, a colorless oil. The structure of the reaction product is verified by NMR analysis.

Aufarbeitung

  1. temperaturemaintained
  2. temperatureat reflux
  3. temperaturethe reaction mixture is heated
  4. temperatureat reflux for 45 minutes
  5. temperatureto cool slowly to room temperature
  6. customafter concentration of the organic solution, the crude product is purified by flash chromatography on silica gel with 20:1 heptane-ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-7ec03ed4c221450393ab7998fdf397b8
Quelldatensatz
uspto-grants-2008_06
Patentnummer
US07390904B2

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